*********************************
There is now a CONTENT FREEZE for Mercury while we switch to a new platform. It began on Friday, March 10 at 6pm and will end on Wednesday, March 15 at noon. No new content can be created during this time, but all material in the system as of the beginning of the freeze will be migrated to the new platform, including users and groups. Functionally the new site is identical to the old one. webteam@gatech.edu
*********************************
Prof. Tim Warren, Georgetown University
Discrete Late Metal Nitrenes in Catalytic C-H Amination
Catalytic C-H amination offers the opportunity to directly convert C-H bonds into amine functionalities without the need for prior chemical modification of these normally unreactive C-H bonds. Electrophilic, late transition metal-nitrene complexes [M]=NR are believed to be the active intermediates in this challenging transformation, providing greater chemoselectivity than free nitrenes themselves. Using well-defined -diketiminato complexes of Co, Ni, and Cu, we demonstrate the synthesis of discrete metal-nitrene complexes which enables a detailed examination of their electronic structure as well as reactivity towards a variety of substrates. These fundamental inorganic synthetic studies allow for the rational development of a catalytic system for the efficient amination of a wide variety of sp3-hybridized C-H bonds with organoazides.
Leading References:
(1) "Transient Terminal Cu-Nitrene Intermediates from Discrete Dicopper Nitrenes" Badiei, Y. M.; Krishnaswamy, A.; Melzer, M.; Warren, T. H. J. Am. Chem. Soc. 2006, 128, 15056-15057.
(2) "A Terminal Ni(III)-Imide with Diverse Reactvity Pathways" Kogut, E.; Wiencko, H. L.; Zhang, L.; Cordeau, D. C.; Warren, T. H.* J. Am. Chem. Soc. 2005, 127, 11248-11249.
(3) "[Me2NN]Co(6-toluene): O=O, O=N, and N=N Bond Cleavage Provides -Diketiminato -Oxo and Imido Complexes" Dai, X.; Kapoor, P.; Warren, T. H. J. Am. Chem. Soc. 2004, 126, 4798-4799.
For more information contact Dr. Jean-Luc Bredas (404-385-4986).
